JP4059679B2 - Method for purifying carbonyl difluoride - Google Patents
Method for purifying carbonyl difluoride Download PDFInfo
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- JP4059679B2 JP4059679B2 JP2002022627A JP2002022627A JP4059679B2 JP 4059679 B2 JP4059679 B2 JP 4059679B2 JP 2002022627 A JP2002022627 A JP 2002022627A JP 2002022627 A JP2002022627 A JP 2002022627A JP 4059679 B2 JP4059679 B2 JP 4059679B2
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- activated carbon
- carbonyl difluoride
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Description
【０００１】
【発明の属する技術分野】
本発明は、有機合成の試薬、半導体製造装置のクリーニングガス、エッチングガス等に有用な二フッ化カルボニル（ＣＯＦ2）の精製方法に関するものである。
【０００２】
【従来の技術および発明が解決しようとする課題】
ＣＯＦ2は、一酸化炭素とフッ素との直接反応により比較的容易に製造可能であるが、この場合生成したＣＯＦ2ガス中には、０．１ｖｏｌ％〜５ｖｏｌ％程度のトリフルオロメチルハイポフルオライト（ＣＦ3ＯＦ）が副生する。ＣＦ3ＯＦは、ＣＯＦ2と比較的沸点が近接しており、蒸留等では完全に除去分離することが困難であり、また、ＣＯＦ2及びＣＦ3ＯＦは、水で加水分解するため水に不活性なガスとの分離は可能であるが、ＣＯＦ2からＣＦ3ＯＦを除去分離する方法については文献等では全く開示されていなかった。
【０００３】
【課題を解決するための手段】
本発明者らは、かかる問題点に鑑み鋭意検討の結果、活性炭を用いてＣＯＦ2中のＣＦ3ＯＦを分離、除去できることを見出し、本発明に到達した。
【０００４】
すなわち、本発明は、少なくともトリフルオロメチルハイポフルオライトを不純物として含む二フッ化カルボニルを、活性炭と接触させることを特徴とする二フッ化カルボニルの精製方法を提供するものである。
【０００５】
本発明によれば、ＣＦ3ＯＦを含有するＣＯＦ2から、ほぼ完全にＣＦ3ＯＦを分離精製することが可能となる。
【０００６】
【発明の実施の形態】
本発明において、使用可能な活性炭は、通常市販されている活性炭を適宜選択すればよいが、ＣＯＦ2が非常に加水分解し易い物質であるため、水分、あるいは水酸基をできるだけ含まないような活性炭が好ましい。また、ＣＦ3ＯＦは、酸化力を有しており、活性炭に含まれる不純物を酸化して揮発性のフッ化物を生成しやすいため、珪素、砒素、リン、ホウ素、窒素、硫黄、塩素等の元素を含まない活性炭が好ましい。
【０００７】
活性炭は、使用する前に水分を完全に除去するために、できる限り乾燥することが好ましい。水分を効率的に除去するために、３００℃以上で真空乾燥することが好ましい。
【０００８】
活性炭とＣＦ3ＯＦを含有するＣＯＦ2を接触させるときの温度としては、−８５℃以上１００℃未満で適宜選択すればよいが、通常室温付近が操作性が良く好ましい。−８５℃より低い温度では、ＣＯＦ2が液化し、１００℃以上の温度では、ＣＦ3ＯＦの吸着能力が低下するため好ましくない。
【０００９】
活性炭と接触させるときの圧力は、適宜選択すれば良いが、通常大気圧付近が操作性が良く好ましい。
【００１０】
活性炭との接触方法は、封入法、流通法のいずれを用いても良いが、生産性の面から流通法が好ましい。
【００１１】
本発明において、活性炭で精製する前に、あらかじめＣＯＦ2を封入して、活性炭を前処理することにより、活性炭に含まれる微量な水分等を反応除去でき、ＣＯＦ2の純度を向上することができる。前処理は室温でも可能であるが、１００℃以上の温度でＣＯＦ2処理すると、より効果的である。また、活性炭中に前述のような不純物が含有している場合には、あらかじめＣＦ3ＯＦを吸着、反応させた後、３００℃以上で真空脱気してＣＦ3ＯＦの脱着を行ってから使用するのが好ましい。
【００１２】
【実施例】
以下、本発明を実施例により詳細に説明するが、本発明はかかる実施例に限定されるものではない。
【００１３】
実施例１
φ１／２インチ×７０ｃｍのステンレス鋼製チューブ（容量６３ｍｌ）に、活性炭（和光純薬製、顆粒状）を６０ｇ仕込み精製塔とした。この精製塔を３００℃で２時間真空加熱処理した後、ヘリウムで置換し、室温まで降温した。真空状態とした精製塔に、１．１ｖｏｌ％のＣＦ3ＯＦが含有するＣＯＦ2を１０１ＫＰａ導入し、５分間放置した。精製塔内部のガスをサンプリングしＧＣ−ＭＳで分析した結果、ＣＦ3ＯＦは検出されなかったが０．０５％のＳｉＦ4が検出された。
【００１４】
実施例２
実施例１で使用した精製塔にＣＦ3ＯＦを１０１ＫＰａまで導入し、２時間放置した。更に、この精製塔を真空引きしてＣＦ3ＯＦを脱着しつつ、３００℃まで昇温し完全にＣＦ3ＯＦを脱着させた。この精製塔をヘリウムで置換した後、室温まで降温し、真空状態とした。１．１ｖｏｌ％のＣＦ3ＯＦが含有するＣＯＦ2を１０１ＫＰａ導入し、５分間放置した。精製塔内部のガスをサンプリングしＧＣ−ＭＳで分析した結果、ＣＦ3ＯＦは検出されず、ＳｉＦ4についても検出されなくなった。
【００１５】
実施例３
実施例２で使用した精製塔を３００℃で２時間真空脱気を行い、ヘリウムで置換後降温した。この精製塔に、室温、１０１ＫＰａ、流量２０ｓｃｃｍの条件で、１．１ｖｏｌ％のＣＦ3ＯＦが含有するＣＯＦ2を２時間流通させた。精製したガスは１Ｌ−トラップに液体窒素温度で捕集し、ＧＣ−ＭＳで分析した結果、ＣＦ3ＯＦ、ＳｉＦ4は検出されず、ＣＯＦ2の回収率は９０％であった。
【００１６】
【発明の効果】
本発明によると、ＣＯＦ2中のＣＦ3ＯＦを簡便に除去でき、高純度で高回収率で、しかも生産性良くＣＯＦ2を精製することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for purifying carbonyl difluoride (COF 2 ) useful as a reagent for organic synthesis, a cleaning gas for semiconductor manufacturing equipment, an etching gas, and the like.
[0002]
[Background Art and Problems to be Solved by the Invention]
COF 2 can be produced relatively easily by a direct reaction between carbon monoxide and fluorine. In this case, the generated COF 2 gas contains about 0.1 vol% to 5 vol% of trifluoromethyl hypofluorite. (CF 3 OF) is by-produced. CF 3 OF are relatively close boiling point and COF 2, it is difficult to completely remove separated by distillation or the like, also, COF 2 and CF 3 OF are not in water to hydrolyze with water Although separation from active gas is possible, a method for removing and separating CF 3 OF from COF 2 has never been disclosed in the literature.
[0003]
[Means for Solving the Problems]
As a result of intensive studies in view of such problems, the inventors have found that CF 3 OF in COF 2 can be separated and removed using activated carbon, and have reached the present invention.
[0004]
That is, the present invention provides a method for purifying carbonyl difluoride, which comprises contacting carbonyl difluoride containing at least trifluoromethyl hypofluorite as an impurity with activated carbon.
[0005]
According to the present invention, the COF 2 containing CF 3 OF, it is possible to almost completely separate the CF 3 OF purification.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the activated carbon that can be used may be appropriately selected from commercially available activated carbon. However, since COF 2 is a substance that is very easily hydrolyzed, activated carbon that contains as little water or hydroxyl groups as possible is used. preferable. In addition, CF 3 OF has an oxidizing power and easily oxidizes impurities contained in activated carbon to generate volatile fluorides. Therefore, such as silicon, arsenic, phosphorus, boron, nitrogen, sulfur, chlorine, etc. Activated carbon containing no elements is preferred.
[0007]
The activated carbon is preferably dried as much as possible in order to completely remove moisture before use. In order to remove moisture efficiently, vacuum drying is preferably performed at 300 ° C. or higher.
[0008]
The temperature at which activated carbon and COF 2 containing CF 3 OF are brought into contact with each other may be appropriately selected between −85 ° C. and less than 100 ° C., but usually near room temperature is preferable because of good operability. When the temperature is lower than −85 ° C., COF 2 is liquefied, and when the temperature is 100 ° C. or higher, the adsorption capacity of CF 3 OF is not preferable.
[0009]
The pressure at which the activated carbon is brought into contact may be selected as appropriate, but usually near atmospheric pressure is preferable because of good operability.
[0010]
As the contact method with activated carbon, either the enclosing method or the distribution method may be used, but the distribution method is preferable from the viewpoint of productivity.
[0011]
In the present invention, before purifying with activated carbon, COF 2 is encapsulated in advance and the activated carbon is pretreated, whereby a trace amount of water contained in the activated carbon can be removed by reaction, and the purity of COF 2 can be improved. . The pretreatment can be performed at room temperature, but it is more effective if the COF 2 treatment is performed at a temperature of 100 ° C. or higher. If activated carbon contains impurities such as those mentioned above, CF 3 OF is adsorbed and reacted in advance, and then vacuum degassed at 300 ° C. or higher to desorb CF 3 OF before use. It is preferable to do this.
[0012]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this Example.
[0013]
Example 1
A refined tower was prepared by charging 60 g of activated carbon (manufactured by Wako Pure Chemical Industries, granule) into a stainless steel tube (capacity 63 ml) of φ1 / 2 inch × 70 cm. This purification tower was subjected to vacuum heat treatment at 300 ° C. for 2 hours, then replaced with helium, and the temperature was lowered to room temperature. 101 KPa of COF 2 containing 1.1 vol% CF 3 OF was introduced into the vacuum purification column and left for 5 minutes. As a result of sampling the gas inside the purification tower and analyzing by GC-MS, CF 3 OF was not detected but 0.05% SiF 4 was detected.
[0014]
Example 2
CF 3 OF was introduced to 101 KPa in the purification tower used in Example 1, and left for 2 hours. Further, the purification tower was evacuated to desorb CF 3 OF, and the temperature was raised to 300 ° C. to completely desorb CF 3 OF. After this purification tower was replaced with helium, the temperature was lowered to room temperature and a vacuum was applied. COF 2 containing 1.1 vol% CF 3 OF was introduced at 101 KPa and left for 5 minutes. As a result of sampling the gas inside the purification tower and analyzing by GC-MS, CF 3 OF was not detected, and SiF 4 was not detected.
[0015]
Example 3
The purification tower used in Example 2 was vacuum degassed at 300 ° C. for 2 hours, replaced with helium, and then cooled. Through this purification tower, COF 2 containing 1.1 vol% CF 3 OF was passed for 2 hours under the conditions of room temperature, 101 KPa, and flow rate of 20 sccm. The purified gas was collected in a 1 L-trap at a liquid nitrogen temperature and analyzed by GC-MS. As a result, CF 3 OF and SiF 4 were not detected, and the recovery rate of COF 2 was 90%.
[0016]
【The invention's effect】
According to the present invention, CF 3 OF in COF 2 can be easily removed, and COF 2 can be purified with high purity, high recovery rate, and high productivity.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002022627A JP4059679B2 (en) | 2002-01-31 | 2002-01-31 | Method for purifying carbonyl difluoride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002022627A JP4059679B2 (en) | 2002-01-31 | 2002-01-31 | Method for purifying carbonyl difluoride |
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| Publication Number | Publication Date |
|---|---|
| JP2003221213A JP2003221213A (en) | 2003-08-05 |
| JP4059679B2 true JP4059679B2 (en) | 2008-03-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002022627A Expired - Fee Related JP4059679B2 (en) | 2002-01-31 | 2002-01-31 | Method for purifying carbonyl difluoride |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4415656B2 (en) * | 2003-11-26 | 2010-02-17 | ダイキン工業株式会社 | Method for purifying carbonyl difluoride |
| JP2006282398A (en) * | 2004-01-26 | 2006-10-19 | Daikin Ind Ltd | Method for refining carbonyl difluoride |
| JP4859384B2 (en) * | 2005-04-05 | 2012-01-25 | 関東電化工業株式会社 | Metal fluoride deoxidizer and method for producing the same |
| KR101395423B1 (en) | 2009-10-27 | 2014-05-14 | 쇼와 덴코 가부시키가이샤 | Method for purification of fluorine-containing compound |
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